1, 1-dihalo-butadiene-1, 3 nematocides



United States Patent 3,139,377 1,1-DIHALO-BUTADENE-L3 NEMATOCIDESKenneth W. Ratts, Creve Coeur, Mo., assignor to Monsanto Company, acorporation of Delaware No Drawing. Filed Feb. 18, 1963, Ser. No.259,402 5 Claims. (Cl. 167-30) This invention relates to a method ofdestroying nematode parasites employing as the essential activeingredient at least one 1,1-dihalo-butadiene-1,3 of the formula whereinX and Y are like or unlike halogens of atomic weight in the range of 35to 80' (i.e. chlorine or bromine), wherein Z is halogen of atomic weightin the range of 18 to 80 (i.e. fluorine, chlorine or bromine), wherein mis an integer from 0 to 2, wherein n is an integer from O to 3, andwherein the sum of m and n is an integer from O to 3.

The 1,l-dihalo-butadiene-1,3 compounds of this invention can be preparedby reacting a triphenylphosphinedihalomethylene of the formula /Y (Css)s wherein Y and Z have the aforedescribed significance with acinnamaldehyde or mixtures thereof of the formula wherein X, m and n hasthe aforedescribed significance in an inert anhydrous organic liquidmedium.

These triphenylphosphine dihalomethylene precursors are prepared byadding a haloform (e.g. chloroform, bromoform, fluorodichloromethane orbromodichloromethane) to a suspension of triphenylphosphine andpotassium t-butoxide in an inert anhydrous organic liquid hydrocarbonmedium at a temperature of about 0 to C. It is preferred not to separatethe resulting triphenylphosphinedihalomethylene (a yellow solid in allinstances) because of its reactivity with water but to add theappropriate benzaldehyde or mixtures thereof to the resulting reactionmass or concentrate thereof and thereafter recover the resulting1,1-dihalo-butadiene-1,3. As illustrative of the preparation of the1,1-dihalo-butadiene- 1,3 nematocides of this invention is thefollowing:

Example I 12 parts by weight of chloroform in about 140 parts by weightof heptane is added over a 30 minute period to a well-agitated,ice-cooled mixture of 26.2 parts by Weight of triphenylphosphine and11.2 parts by weight of anhydrous potassium t-butoxide in about 210parts by weight of heptane. The resulting yellow suspension oftrihpenylphosphinedichloromethylene, i.e.

is then concentrated to about 100 parts by volume by vacuum distillingat about 15-20 C. To this concentrate is added 13.2 parts by weight ofcinnamaldehyde in about 150 parts by weight of heptane. The reactionmass is then maintained at -25 C. while agitating for about 6 hours. Theresulting mixture is filtered and the filter 3,139,377. Patented June30, 1964 Employing the procedure of Example I but replacingcinnamaldehyde with an equimolecular amount of p-nitrocinnamaldehydethere is obtained 1,1-dichloro-4-(4- nitrophenyl) -butadiene-1,3

Example Ill Employing the procedure of Example I but replacingchloroform with an equimolecular amount of bromoform there is obtainedsolid 1,l-dibrom.o-4-(phenyl)- butadiene-1,3. In this instance theintermediary phos phinedihalomethylene is yellow solidtriphenylphosphinedibromoethylene, i.e (C H P CBr Example IV Employingthe procedure of Example I but replacing chloroform with anequimolecular amount of bromodichloromethane there is obtained solidl-chloro-l-bromo- 4-(phenyl)-butadiene-1,3. In this instance theintermediary phosphinedihalornethylene is yellow solidtriphenylphosphinechlorobromomethylene, i.e.

(C H P=CBrCl Example V Employing the procedure of Example I butreplacing cinnamaldehyde with an equimolecular amount of m,pdichlorocinnamaldehyde there is obtained 1,1-dich1oro- 4- 3,4-dichlorophenyl) -butadiene-1,3.

In like manner the following 1,1-dihalo-butadiene-l,3 nematocides andmixtures thereof are prepared from the appropriatetriphenylphosphinedihalomethylene and the appropriate cinnamaldehyde ormixtures thereof 1-chloro-1-fluoro-4-(phenyl) -butadiene-1,31,1-dich1oro-4-(3-chlorophenyl)-butadiene-1,3 1,1-dichloro-4-(4chlorophenyl) -butadiene-1,3 1,1-dichloro-4-(2,4-dichlorophenyl) -butadiene-1,3

, -dichloro-4- (2,4,5 -trichlorophenyl) -butadiene-1 ,3 dichloro-4-(2,4,6-trichlorophenyl) -butadiene-1,3 dichloro-4- (Z-nitrophenyl)-butadienel ,3 dichloro-4-(2,4-dinitrophenyl) -butadiene-1,3 dichloro-4-(2-chloro-4-nitrophenyl) -butadiene-l ,3 -dichloro-4-('2-nitro-4chlorophenyl) -butadiene-1,3

ll 11 ll 11 1,1 1,1 11 11 11 11 1 As aforementioned the1,1-dihalo-butadiene-l,3 compounds of this invention are effective indestroying nematodes. For example (1) to an aqueous suspensioncontaining 3 ppm. of 1,1-dichloro-4-(phenyl)-butadiene-l,3 in a glassvial is added freshly hatched larvae of the vinegar eel Worm, Turbatrixaceti, and the vial stoppered. After 24 hours at room temperaturecomplete destruction was observed;

(2) to approximately 400 grams of a sandy loam soil infested with thelarvae of the tomato root knot nematode, Meloid'ogyne javanica, is addedand intimately mixed with 0.150 grams of 1,1-dichloro-4-(phenyl)-butadiene-1,3. This mixture is placed in a one pint Mason jar, the jarcapped, and permitted to stand for 7 days at room temperature. The soilis then potted and allowed to aerate for 7 days. Seedling tomato plants(Improved Pearson) are then transplated in the aerated potted soil.After 4 weeks the plants were removed and examination thereof showed nonematode damage. In contrast the control plants were severly damaged bythe nematodes.

The soil-phase of other nematode parasites, such as the sugar beetnematode Heterodera schachtii, is also effectively controlled byincorporating in soil infested with same the 1,1-dihalo-butadiene-1,3compounds of this invention, and a particularly useful class ofnematocidal 1,1-dihalo-butadiene-1,3 compounds for this purpose arethose of the formula wherein m is an integer from to 2, and wherein Yand Z are halogens of atomic weight in the range of 35 to 80, e.g.1,1-dibromo-4-(phenyl)-butadiene-l,3;1,1-dichloro-4-(4-nitrophenyl)-butadiene-1,3, and 1,1-dichloro- 4-(2,4-dinitrophenyl) -butadiene-1, 3

In actual usage any of the 1,1-dihalo-butadiene-1,3 compounds of thisinvention or mixtures thereof are added to the soil in solution, as anemulsion or water dispersion but preferably is added in a solidformulation wherein the active nematocide is distributed over some dryand permanently free-flowing powder such as the clays, includingbentonite and attapulgite or such materials as talc, diatomaceous earth,fullers earth, chalk, calcium carbonate and the like. These diluentspossess the added advantage of lower cost treatment since the soil atrates of 5 to 100 pounds per acre. The preferred application fortreating soils of average nematode infestation will be from 10 to 50pounds per acre. The formulation may contain dispersants which aiduniform distribution.

While this invention has been described with respect to certainembodiments, it is to be understood that it is not so limited and thatvariations and modifications thereof obvious to those skilled in the artcan be made without departing from the spirit and scope thereof.

What is claimed is:

1. The method of destroying nematode parasites which comprisescontacting the nematode parasite with a 1,1- dihalo-butadiene-1,3 of theformula wherein Z is halogen of atomic weight in the range of mulanormally they comprise more than up to 98% of the complete formulationand thereby provide a means of more even distribution of the activematerial over a wider area and in the effective quantities required.These nematocidal compositions will of course attack the soil phase ofthe life cycle of nematode parasites which infest animals. Treatingbarnyards, chicken pens, stable and other infested areas destroys eggsand infestive larvae of many parasites which infest animals. Moreover,the compositions are effective for the control of nematodes in theirenvironment which includes bodies of animals.

In the use of 1,1-dihalo-butadiene-1,3 compounds of this invention asnematocides or soil fumigants the active compound, diluted or undiluted,may be applied to range of 35 to and wherein m is an integer from 0 t02'.

3. The method of destroying the soil phase of nematode parasites whichcomprises incorporating in the nematode infested soill,1-dichloro4-(phenyl)-butadiene-l,3.

4. The method of destroying the soil phase of nematode parasites whichcomprises incorporating in the nematode infested soil1,1-dibromo-4-(phenyl)-butadiene-1,3.

5. The method of destroying the soil phase of nematode parasites in aninfested agricultural soil which comprises incorporating in the soil ata rate of 5 to pounds per acre a 1,l-dihalo-butadiene-1,3 of the formula/Y CH=OHCH=O (N na wherein m is an integer from 0 to 2 and wherein Y andZ are halogens of atomic weight in the range of 35 to 80.

References Cited in the file of this patent UNITED STATES PATENTS2,312,801 Craig et al. Mar. 2, 1942 2,456,061 Cass Mar. 22, 19492,714,619 Anderegg et al. Aug. 2, 1955 2,839,096 Lane Apr. 8, 19582,849,503 Eberly et al Aug. 26, 1958

1. THE METHOD OF DESTROYING NEMATODE PARASITES WHICH COMPRISESCONTACTING THE NEMATODE PARASITE WITH A DIHALO-BUTADIENE-1,3 OF THEFORMULA